Styrene caustic wash extraction aid

ABSTRACT

Methods and compositions for improving the extraction of phenols from crude styrene using an aqueous caustic solution are disclosed. It has been discovered that aromatic or alkylammonium tailed multi-polyether headed surfactants and/or quaternary polyamines will improve this extraction, particularly in propylene oxide styrene monomer systems.

FIELD OF THE INVENTION

The present invention provides for methods for improving the extractionof phenols in the propylene oxide styrene monomer process. Morespecifically, the present invention provides for methods for improvingthe removal of phenols from crude styrene with aqueous caustic.

BACKGROUND OF THE INVENTION

In the propylene oxide styrene monomer (POSM) process, methyl oxirane(propylene oxide) and ethenyl or vinyl benzene (styrene monomer) areco-produced. Molecular oxygen is reacted with ethylbenzene to formα-hydroperoxy ethylbenzene which is then subsequently reacted withpropene to form propylene oxide and α-hydroxyethylbenzene, also known asmethylbenzyl alcohol.

After removing the more volatile propylene oxide, the methylbenzylalcohol is dehydrated to water and styrene monomer. These areco-distilled overhead and condensed into a water/oil separator, wherethe water forms a separate phase and is drained. The crude styrene phaseis then extracted in a caustic wash drum with 5 to 10% of an aqueouscaustic solution containing about 2 to 3% NaOH, sometimes with about anequal amount of a caustic solution recycled to remove phenolicbyproducts of the above-described oxidation and epoxidation reactions.

The caustic extracted styrene is then rinsed in a water wash drum with 5to 10% fresh water, also sometimes with about an equal amount recycled,to remove residual caustic and phenate salts from the crude styreneprior to distillation. Typically, the temperature of the extraction isabout 100 to 110° F. The pH in the second stage is about 11.5 and in thefirst stage is about 14.

The present inventor has discovered a means to improve this extractionprocess while minimizing residual carryover of caustic and phenates tothe styrene distillation towers. This method also helps eliminate theproduction and disposal as toxic waste of stable dispersion layers whichotherwise accumulate in separation vessels.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides for an improved method for extractingphenols from crude styrene with aqueous caustic, the improvementcomprising adding to the styrene an effective amount for the purpose ofaiding extraction of an aromatic or alkylammonium tailed multi-polyetherheaded surfactant or a quaternary polyamine.

The aromatic or alkylammonium tailed multi-polyether headed surfactants(MPEHS) include those with hydrophobic "tails" comprising C₃ to C₁₈alkylaryl diols to polyols and C₃ to C₂₂ alkyl or alkylaryl 1° or 2°amines. These are adducted with C₂ to C₃ alkylene oxides to form two ormore hydrophilic heads per hydrophobe comprising separate polyetherchains of degree of polymerization (dp) 3 to 30. The backbone andbranches of the polymer contain only ether or amine linkages, and not,for example, esters or amides. Quaternary amines employ any convenientcounterions, such as halides, sulfates, nitrates, phosphates,carboxylates, phenates, silicates, carbonates, or hydroxides.

Preferably, the multi-polyether headed surfactant comprises C₄ to C₉alkylphenol-formaldehyde condensates of dp 4 to 8 adducted with ethyleneoxide to form 4 to 8 polyether chains of dp 4 to 7 blended with thehalide salt of linear C₁₂ to C₂₂ alkyl 2° amines adducted with ethyleneoxide to form 2 polyether chains of dp 5 to 10.

The quaternary polyamines used in the present invention are those inwhich the backbone and branches of the polymer contain only ether oramine linkages and not, for example, esters or amides. The polyamineshould have a degree of polymerization of about 60 to 6000 monomer unitsand an overall carbon to nitrogen or oxygen ratio of less than 10. Thesecompounds are water soluble.

The quaternary polyamines include but are not limited to halides,sulfates, nitrates, phosphates, carboxylates, phenates, silicates,carbonates, or hydroxides of alkyl or alkylaryl quaternary amines. Thepreferred polyamines include but are not limited topoly(diallydimethylammonium chloride), or poly(DADMAC), having theformula: ##STR1## poly(N,N-dimethyl, 2-hydroxypropyleneammoniumchloride), or poly(DMHPAC), having the formula: ##STR2## andpoly(N,N-dimethyl, 3-(2-hydroxypropyleneamine) propylammonium chloride),or poly[DM(HPA)PAC], having the formula: ##STR3##

The poly(DMHPAC) compound may be formed by reacting about equimolaramounts of 3-chloromethyl-1,2-oxirane (epichlorohydrin of EPI) withdimethylamine (DMA).

The poly[DM(HPA)PAC] may be formed by reacting about equimolar amountsof EPI and dimethylaminopropylamine (DMAPA).

The present inventor has discovered that these extraction aids assist influidizing, solubilizing and removing the surfactant barrier to improveextraction efficiency. This minimizes the caustic carryover to the crudestyrene distillation section and eliminates the production and disposalof the dispersion layer.

The multi-polyether headed surfactants are preferably fed as solutionsin aqueous or organic solvents that are compatible with both the MPEH'sand the POSM process. The organic solvents include high boiling (i.e.greater than 400° F.) aromatic hydrocarbons, glycol ethers, such as2-n-butoxy-2-ethoxyethanol (butyl carbitol), and native aromaticalcohols such as α-hydroxyethylbenzene, which is most preferred.

Preferably the solutions are fed to the influent, unwashed styrene. Thesolutions may also be fed to the interstage, washed but not rinsedstyrene. Preferably from about 3 to about 30 parts of MPEH per millionparts of styrene are fed.

The quaternary polyamines are preferably fed an aqueous solution to theinfluent caustic wash water or the fresh rinse water or most preferablyboth the caustic wash and rinse water, prior to mixing with the styrene.

The quaternary polyamines are fed in amounts ranging from about 1 partto about 100 parts polyamine per million parts of water with a range ofabout 3 to about 30 preferred, or about 0.1 part to about 10 parts permillion parts of styrene with a range of about 0.2 to about 2.0 partspreferred.

The following examples are intended to show the efficacy of the presentinvention and should not be construes as limiting the scope of theinvention.

EXAMPLES

In order to find a counteractant to the barrier soaps, which tend toaccumulate at the interface of the extraction vessels, a sample ofconcentrated soap in an 18% oil-in-water emulsion from the second stageof a Southwestern U.S. POSM caustic wash unit was taken.

Selected candidates were screened using the following procedure:

1. Add 100 mL of sample to 6 oz. Rx bottle

2. Heat the bottle to 105° F. in a 105° F. water bath

3. Treat the sample with chemical at 105° F.

4. Shake the bottle with a 3 inch stroke at 60 cps for 1 minute on amechanical shaker

5. Place the bottle back into a 105° F. bath

6. Record rate and degree to which soapy appearance disappears.

Table A lists the chemicals that were tested.

TABLE A

A Branched nonylphenol-formaldehyde condensate of dp 4-8 adducted withpropyl- and ethylene oxides to form 4-8 polyether chains of dp 7-10 each

B 2,2-bis-p-phenoxyhydroxypropyletherpoly(propylether) propane of dp 0-2adducted with ethylene oxide to form 4-8 polyether chains of dp 4-8 each

C Poly(N,N-dimethyl, 2-hydroxypropyleneammonium and3-(2-hydroxypropyleneamine) propylammonium, chlorides)

D Poly(diallydimethyl ammonium chloride)

The results of this screening are shown in Tables I & II. The "top oil"described as "opaque white" was found to be a water continuous phase."Translucent" (or "transluc.") and "transparent" (or "transpar.")indicate an oil continuous phase, with and without significant entrainedwater, respectively. "Transparent" indicates text is readable throughthe phase, though some dispersed material remains. "Clear" indicatesphase is substantially free of any dispersed material. Within a givenopacity classification, the color indicates the relative amount offoreign material present in the phase, withbrown>tan>amber>yellow>white.

                                      TABLE I                                     __________________________________________________________________________            Post-Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   30 Minutes  60 Minutes                                    Chemi-                                                                            ppm     Bottom      Bottom      Bottom                                      cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F               __________________________________________________________________________    blank                                                                             0   opaque                                                                            opaque                                                                            much                                                                              opaque                                                                            opaque                                                                            much                                                                              opaque                                                                            opaque                                                                            much                                      white white soap white white soap white white soap                          A 3 opaque opaque much opaque opaque much opaque opaque much                    white white soap white white soap white white soap                          A 7.5 opaque opaque much opaque opaque much opaque opaque much                  white white soap white white soap white white soap                          A 15 opaque opaque much opaque opaque much opaque opaque much                   white white soap white white soap white white soap                          A 30 opaque opaque much opaque opaque much opaque opaque much                   white white soap white white soap white white soap                          A 60 opaque opaque much opaque opaque much opaque opaque much                   white white soap white white soap white white soap                          A 120 opaque opaque much opaque opaque much opaque opaque much                  white white soap white white soap white white soap                          A 240 opaque opaque much opaque opaque much opaque opaque much                  white white soap white white soap white white soap                          C 1.5 50% trans- much 75% trans- much 80% opaque much                           trans- lucent soap trans- lucent soap trans- white soap                       luc.   luc.   parent                                                          brown   brown                                                               C 3.75 80% trans- little 90% trans- little 90% trans- much                      trans- lucent soap trans- parent soap trans- lucent soap                      luc.   luc.   par.                                                            brown   brown   amber                                                       C 7.5 all trans- no 100% trans- no 100% trans- no                               trans- parent soap trans- parent soap trans- parent soap                      luc.   par.   par.                                                            brown                                                                       C 15 25% trans- much 50% trans- much 80% trans- much                            trans- parent soap trans- parent soap trans- parent soap                      parent,   parent   parent                                                   C 30 opaque trans- much opaque trans- much 25% trans- much                      white lucent soap white lucent soap trans- lucent soap                              parent                                                                C 60 opaque opaque much opaque opaque much 10% opaque much                      white white soap white white soap trans- white soap                                 parent                                                                C 120 opaque opaque much opaque opaque much 10% opaque much                     white white soap white white soap trans- white soap                                 parent                                                                D 1.5 opaque opaque much opaque opaque much 10% opaque much                     white white soap white white soap trans- white soap                                 parent                                                                 3.75 opaque opaque much 25% opaque much 25% opaque much                        white white soap trans- white soap trans- white soap                             luc.   parent                                                                 brown                                                                    D 7.5 50% opaque much 50% opaque much 50% opaque much                           trans- white soap trans- white soap trans- white soap                         luc.   luc.   par.                                                            brown   brown   amber                                                       D 15 90% trans- little 90% clear little 90% clear little                        trans- parent soap trans-  soap trans-  soap                                  luc.   iuc.   parent                                                          brown   brown                                                               D 30 25% trans- much 50% trans- much 50% trans- much                            trans- parent soap trans- parent soap trans- parent soap                      luc.   luc.   parent                                                          brown   brown                                                               D 60 opaque trans- much opaque trans- much much opaque much                     white lucent soap white lucent soap soap white soap                         D 120 opaque trans- much opaque trans- much much opaque much                    white lucent soap white lucent soap soap white soap                       __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________            Post Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   15 Minutes  30 Minutes  60 Minutes                        Chemi-                                                                            ppm     Bottom      Bottom      Bottom      Bottom                          cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F Top Oil                                                            Water I/F                __________________________________________________________________________    blank                                                                             0   opaque                                                                            opaque                                                                            much                                                                              opaque                                                                            opaque                                                                            little                                                                            opaque                                                                            opaque                                                                            little                                                                            opaque                                                                            opaque                                                                            little                        white white soap white white soap white white soap white white soap                                                            B 2.3 opaque opaque                                                          much opaque opaque                                                            little opaque trans-                                                          little opaque opaque                                                          little                        white white soap white white soap white lucent soap white white soap                                                           B 4.6 opaque opaque                                                          much opaque opaque                                                            little opaque trans-                                                          little opaque opaque                                                          little                        white white soap white white soap white lucent soap white white soap                                                           B 9.2 opaque opaque                                                          much opaque opaque                                                            little opaque trans-                                                          little opaque opaque                                                          little                        white white soap white white soap white lucent soap white white soap                                                           B 18.4 opaque opaque                                                         much opaque opaque                                                            little opaque trans-                                                          little opaque opaque                                                          little                        white white soap white white soap white lucent soap white white soap                                                           B 36.5 opaque opaque                                                         much opaque opaque                                                            tittte opaque trans-                                                          little opaque opaque                                                          little                        white white soap white white soap white lucent soap white white soap                                                           B 73.6 opaque opaque                                                         much opaque opaque                                                            little opaque trans-                                                          little opaque opaque                                                          little                        white white soap white white soap white lucent soap white white           __________________________________________________________________________                                                        soap                  

Tables I and II show that D from 1.5 to 30 ppm active and, even more soC, from 1.5 to 60 ppm active, per emulsion, were able to remove thebarrier surfactants and allow the dispersed crude styrene to coalesceinto a recoverable, phenate and caustic depleted, clear organic phase ontop, an emulsion free interface between the oil and water layers and aclearer, less wasteful and hazardous water layer. The MPEH's, which havebroken other types of emulsions not containing synthetic stabilizers inother applications at near neutral pH (5-9), had no significant effecton accumulated surfactants such as these at alkaline pH (11-14).

These results imply that the phenol extraction process would be improvedby feeding about 9 ppm of C per water (0-6 ppm active per oil at 6.6%water wash) into the water to the vessel accumulating soapy emulsion.The sample above was taken from stage 2 but if the treatment wereapplied either additionally or instead to stage 1 to keep soap fromcarrying over, better extraction may result.

A second test was run to test an agent's ability to promote formation ofan emulsion with which to extract the phenol but which would also notimpede the reaction of the phenols with the caustic, the transfer of thephenate to the water droplets, or the subsequent coalescence and removalof the droplets from the styrene. Samples of the first stage crudestyrene effluent and the first stage caustic brine effluent (containing0.8% sodium hydroxide and 0.5% sodium phenates) were taken and used torecreate the first stage extraction step in the laboratory. A variety ofcandidate extraction aids were screened using the following procedure:

1. Pour 86 mL crude styrene and 14 mL caustic water into Rx bottle

2. Heat to 105° F. in a water bath

3. Treat with chemical at 105° F. in duplicate

4. Shake the bottle with a 3 inch stroke at 240 cps for 1 minute on amechanical shaker

5. Place the bottle into 105° F. bath

6. Record degree to which an initial milky appearance forms

7. Record the rate and degree the milky appearance disappears for 60minutes.

Table B presents the additional chemicals tested.

TABLE B

E Linear dodecylbenzene sulfonic acid, nonylphenol-formaldehydecondensates of dp 4-8 adducted with ethylene oxide to form 4-8 polyetherchains of dp 4-7, and a nonylphenol ethoxylate

F Branched nonylphenol-formaldehyde condensate of dp 4-8 adducted withethylene oxide to form 4-8 polyether chains of dp 4-7 andpoly(propylether diol) adducted with ethylene oxide to form 2 polyetherchains of dp 12-24

G Branched nonylphenol-formaldehyde condensates of dp 4-8 adducted withethylene oxide to form 4-8 polyether chains of dp 4-7

H Branched nonylphenol-formaldehyde condensates of dp 4-8 adducted withethylene oxide to form 4-8 polyether chains of dp 4-7 and halide saltsof linear C₁₂ to C₂₂ alkyl 2° amines adducted with ethylene oxide toform 2 polyether chains of dp 5-10

I Poly(propylether diol) adducted with ethylene oxide to form 2polyether chains of dp 12-24

J Halide and carboxylate slats of linear C₁₂ to C₂₂ alkyl 1° and 2°amines adducted with ethylene oxide to form 2-3 polyether chains of dp1-10

The results of this testing are presented in Tables III to VII.

                                      TABLE III                                   __________________________________________________________________________            Post Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   15 Minutes  30 Minutes  60 Minutes                        Chemi-                                                                            ppm     Bottom      Bottom      Bottom      Bottom                          cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F Top Oil                                                            Water I/F                __________________________________________________________________________    blank                                                                             0   trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                        lucent, lucent, soap lucent, lucent, soap parent lucent, soap parent                                                          parent, soap                  amber brown  amber amber  amber amber  amber amber                          B 5.8 trans- trans- little trans- trans- little trans- trans- little                                                            clear, trans- little                                                             parent, lucent,                                                            soap parent, parent,                                                          soap parent parent,                                                           soap yellow parent,                                                           soap                          amber amber  yellow yellow  yellow yellow   yellow                          B 12 trans- trans- little trans- clear, little trans- trans- little                                                             clear, trans- little                                                             parent, lucent,                                                            soap parent, yellow                                                           soap parent parent,                                                           soap yellow parent,                                                           soap                          amber amber  yellow   yellow yellow   yellow                                B 23 trans- trans- little trans- clear, liftle trans- trans- little                                                             trans- trans- little                                                             lucent, lucent,                                                            soap parent, yeliow                                                           soap parent parent,                                                           soap parent parent,                                                           soap                          amber amber  amber   amber yellow  yellow yellow                            B 46 trans- trans- little trans- clear, little trans- trans- little                                                             trans- trans- little                                                             lucent, lucent,                                                            soap lucent, yellow                                                           soap lucent, parent,                                                          soap lucent parent,                                                           soap                          amber amber  amber   amber yellow  amber yellow                             B 92 trans- trans- little trans- clear, little trans- trans- little                                                             trans- trans- little                                                             lucent, lucent,                                                            soap lucent, yellow                                                           soap lucent, parent,                                                          soap lucent parent,                                                           soap                          brown amber  brown   brown yellow  amber yellow                             B 184 opaque trans- little opaque clear, little trans- trans- little                                                            trans- trans- little                                                             brown lucent, soap                                                         brown yellow soap                                                             lucent, parent, soap                                                          lucent parent, soap                                                               amber     brown                                                           yellow  brown yellow                                                           D 7.5 trans- opaque                                                          little trans- trans-                                                          little trans- trans-                                                          little trans- trans-                                                          little                        lucent, brown soap lucent, lucent, soap lucent, lucent, soap parent                                                           parent, soap                  amber   amber amber  amber amber  amber yellow                              D 15 trans- opaque little trans- clear, little trans- trans- little                                                             trans- trans- little                                                             lucent, brown soap                                                         lucent, yellow soap                                                           lucent, lucent, soap                                                          lucent parent, soap                                                              amber   amber                                                              amber amber  amber                                                            yellow                      D 30 trans- opaque much trans- clear, little trans- trans- little                                                               trans- trans- little                                                             lucent, brown soap                                                         lucent, yellow soap                                                           lucent, lucent, soap                                                          lucent parent, soap                                                              tan   tan   tan                                                            amber  amber yellow                                                            D 60 trans- opaque                                                           much trans- clear                                                             much trans- trans-                                                            much trans- trans-                                                            little                        lucent, brown soap lucent yellow soap lucent, lucent, soap lucent                                                             parent, soap                  brown   brown   tan amber  brown yellow                                     D 120 trans- opaque much trans clear much trans- trans- much trans-                                                             trans- much                   lucent, brown soap lucent yellow soap lucent, lucent, soap lucent                                                             parent, soap                  brown   brown   brown amber  brown yellow                                   D 240 opaque opaque much trans clear much trans- trans- much trans-                                                             trans- much                   brown brown soap lucent yellow soap lucent, lucent, soap lucent                                                               parent, soap                     brown   brown amber  brown yellow                                      __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________            Post Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   30 Minutes  60 Minutes                                    Chemi-                                                                            ppm     Bottom      Bottom      Bottom                                      cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F               __________________________________________________________________________    blank                                                                             0   trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                    lucent, lucent, soap lucent, lucent, soap parent, parent, soap                                                       brown brown  amber amber                                                   amber amber                             B 1.1 trans- trans- little trans- trans- little trans- trans- little                                                   lucent, parent, soap parent,                                               parent, soap parent, parent, soap         amber amber  amber yellow  yellow yellow                                    B 2.3 trans- trans- little trans- trans- little clear, trans- little                                                   parent, parent, soap parent,                                               parent, soap yellow parent, soap                                                 amber amber  yellow yellow                                                 yellow                                  B 5.8 trans- trans- little trans- trans- little clear, trans- little                                                   parent, parent, soap parent,                                               parent, soap yellow parent, soap                                                 amber amber  yellow yellow                                                 yellow                                  B/D 5.8/0.15 trans- trans- little trans- trans- little trans- trans-                                                little                                    parent, parent, soap parent, parent, soap parent, parent, soap                                                       amber yellow  yellow yellow                                                yellow yellow                           B/D 5.8/0.3 trans- trans- little trans- trans- little trans- trans-                                                 little                                    lucent, parent, soap parent, parent, soap parent, parent, soap                                                       amber yellow  yellow yellow                                                yellow yellow                           B/D 5.8/0.6 trans- trans- little trans- trans- little trans- trans-                                                 little                                    lucent, parent, soap parent, parent, soap parent, parent, soap                                                       amber yellow  amber yellow                                                 yellow yellow                           B/D 2.3/0.15 trans- trans- little trans- trans- little trans- trans-                                                little                                    lucent, parent, soap parent, parent, soap parent, parent, soap                                                       amber yellow  amber yellow                                                 yellow yellow                           B/D 2.3/0.3 trans- trans- little trans trans- little trans- trans-                                                  little                                    lucent, parent, soap parent parent, soap parent, parent, soap                                                        amber yellow  amber yellow                                                 yellow yellow                           B/D 2.3/0.6 trans- trans- little trans trans- little trans- trans-                                                  little                                    lucent, parent, soap parent parent, soap parent, parent, soap                                                        amber yellow  amber yellow                                                 yellow yellow                           D 3.8 trans- trans- little trans- trans- little trans- trans- little                                                   lucent, lucent, soap lucent,                                               parent, soap parent, parent, soap         brown amber  amber amber  amber yellow                                    __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________            Post Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   30 Minutes  60 Minutes                                    Chemi-                                                                            ppm     Bottom      Bottom      Bottom                                      cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F               __________________________________________________________________________    blank                                                                             0   trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                    lucent, lucent, soap lucent, lucent, soap parent, parent, soap                                                       amber brown  amber amber                                                   amber amber                             E 8.2 trans- trans- little trans- trans- little trans- trans- little                                                   parent, lucent, soap parent,                                               parent, soap parent, parent, soap         amber amber  yellow yellow  yellow yellow                                   F 6.2 trans- trans- little trans- trans- little trans- trans- little                                                   parent, lucent, soap parent,                                               parent, soap parent, parent, soap         amber amber  yellow yellow  yellow                                          G 6 trans- trans- little almost trans- little clear, trans- little                                                     parent, lucent, soap clear,                                                parent, soap yellow parent, soap                                                 amber amber  yellow yellow                                                 yellow                                  A 6 trans- trans- little clear, trans- little clearer, trans- little                                                   parent, lucent, soap yellow                                                parent, soap yellow parent, soap                                                 amber amber   yellow   yellow                                               H 4 trans- trans- little                                                     clearer, trans- little clearest,                                              trans- least                              parent, lucent, soap yellow parent, soap yellow parent, soap                  amber amber   yellow   yellow                                               J 3 trans- trans- little trans- trans- little almost trans- little                                                     parent, lucent, soap parent,                                               parent, soap clear, parent, soap                                                 amber amber  yellow yellow                                                 yellow yellow                           B 4.6 trans- trans- little trans- trans- little almost trans- little                                                   parent, lucent, soap parent,                                               parent, soap clear, parent, soap                                                 amber amber  yellow yellow                                                 yellow yellow                           I 7.2 trans- trans- little trans- trans- little trans- trans- little                                                   lucent, lucent, soap lucent,                                               lucent, soap lucent, parent, soap         brown amber  amber amber  amber yellow                                    __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________            Post Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   30 Minutes  60 Minutes                                    Chemi-                                                                            ppm     Bottom      Bottom      Bottom                                      cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F               __________________________________________________________________________    C   0.3 trans-                                                                            opaque,                                                                           little                                                                            trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                    lucent, brown soap lucent, lucent, soap parent, parent, soap                  amber   amber amber  amber yellow                                           C 0.6 trans- trans- little trans- trans- little trans- trans- little                                                   lucent, lucent, soap parent,                                               lucent, soap parent, parent, soap         amber amber  amber amber  amber yellow                                      C 1.2 trans- trans- little trans- trans- little trans- trans- little                                                   lucent, lucent, soap parent,                                               lucent, soap parent, parent, soap         amber amber  amber amber  amber yellow                                      C 2.4 trans- trans- little trans- trans- little trans- trans- little                                                   lucent, lucent, soap parent,                                               lucent, soap parent, parent, soap         amber amber  amber amber  amber yellow                                      C 4.8 trans- opaque, little trans- trans- little trans- trans- little                                                  lucent, brown soap parent,                                                 lucent, soap parent, parent, soap         amber   amber amber  amber yellow                                           C 9.6 trans- opaque, little trans- trans- little trans- trans- little                                                  lucent, brown soap lucent,                                                 lucent, soap parent, parent, soap         brown   amber amber  amber yellow                                           B 2.3 trans- trans- little trans- trans- little almost trans- little                                                   parent, lucent, soap parent,                                               parent, soap clear, parent, soap                                                 amber amber  yellow yellow                                                 yellow yellow                           B 4.6 trans- trans- little almost trans- little almost trans- little                                                   parent, lucent, soap clear,                                                parent, soap clear, parent, soap                                                 amber amber  yellow yellow                                                 yellow yellow                           H 2.0 trans- trans- little clear, trans- little clear, trans- no                                                       parent, lucent, soap yellow                                                parent, soap yellow parent, soap                                                 amber amber   yellow   yellow                                               H 4.0 trans- trans- little                                                   clear, trans- little clear,                                                   trans- no                                 parent, lucent, soap, yellow parent, soap yellow parent, soap                                                        amber amber   yellow               __________________________________________________________________________                                            yellow                            

                                      TABLE VII                                   __________________________________________________________________________            Post Treatment Appearance Readings                                    Treatment                                                                             5 Minutes   30 Minutes  60 Minutes                                    Chemi-                                                                            ppm     Bottom      Bottom      Bottom                                      cal Act Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F               __________________________________________________________________________    blank                                                                             0   trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                                                            trans-                                                                            trans-                                                                            little                                    lucent, lucent, soap parent, lucent, soap parent, parent, soap                                                       amber brown  amber amber                                                   amber amber                             A 6 trans- trans- little clear, trans- little clearer, trans- no                                                       parent, tucent, soap yellow                                                parent, soap yellow parent, soap                                                 amber amber   yellow   yellow                                               A/C 6/0.3 trans- trans- little                                               clear, trans- little clearer,                                                 trans- no                                 parent, lucent, soap yellow parent, soap yellow parent, soap                  amber amber   yellow   yellow                                               A/C 6/0.6 trans- trans- little trans- trans- little clear, trans- no                                                   parent, lucent, soap parent,                                               parent, soap yettow parent, soap                                                 amber amber  yellow yellow                                                 yellow                                  A/C 6/0.9 trans- trans- little trans- trans- little trans- trans- no                                                   parent, tucent, soap parent,                                               parent, soap parent, parent, soap         amber amber  amber yellow  yellow yellow                                    H 4 trans- trans- little clear, trans- little clearest, trans- no                                                      parent, lucent, soap yellow                                                parent, soap yellow parent, soap                                                 amber amber   yellow   yellow                                               H/C 4/0.3 trans- trans- little                                               clear, trans- little clearest,                                                trans- no                                 parent, lucent, soap yellow parent, soap yellow parent, soap                  amber amber   yellow   yellow                                               H/C 4/0.6 trans- trans- little trans- trans- little trans- trans- no                                                   parent, lucent, soap parent,                                               parent, soap parent, parent, soap         amber amber  yellow yellow  yelllow yellow                                  H/C 4/0.9 trans- trans- little trans- trans- little trans- trans- no                                                   parent, lucent, soap parent,                                               parent, soap parent, parent, soap         amber amber  yellow yellow  yellow yellow                                   B 4.6 trans- trans- little trans- trans- little atmost trans- no                                                       parent, tucent, soap parent,                                               parent, soap clear, parent, soap                                                 amber amber  yellow yellow                                                 yellow yellow                           B/C 4.6/0.3 trans- trans- little trans- trans- little trans- trans-                                                 little                                    parent, tucent, soap parent, parent, soap parent, parent, soap                                                       amber amber  yellow yellow                                                 yellow yellow                           B/C 4.6/0.6 trans- trans- little trans- trans- little trans- trans-                                                 little                                    parent, lucent, soap parent, parent, soap parent, parent, soap                                                       amber amber  yelloow yellow                                                yellow yellow                           B/C 4.6/0.9 trans- trans- little trans- trans- little trans- trans-                                                 little                                    lucent, tucent, soap parent, parent, soap parent, parent, soap                                                       amber brown  amber yellow                                                  amber yellow                          __________________________________________________________________________

The data in Tables II and IV show that the aromatic tailed MPEH'sachieved the best results for forming a fluid, extractive emulsion ofcaustic-in-styrene.

The data in Table V demonstrate that aromatic and alkylammonium tailedMPEH's were effective while blends of aromatic and alkylammonium tailedMPEH's were even more effective.

The data in Table VI also show the aromatic and alkylammonium tailedMPEH blend to be best based on caustic removal. Table VII demonstratesthat small amounts of a quaternary polyamine can be added in conjunctionwith the aromatic and/or alkylammonium tailed MPEH's without harm to theextraction process.

Clarified top oil from the previous test and additional DI water wereused to simulated the second stage rinse. Additional treatments andcontrols with no further treatment were tested using the followingprocedure:

1. Thief 70 mL clarified top oil from previous test and place in anotherRx bottle.

2. Add 5.25 mL (7%) DI water to 2nd bottle.

3. Heat to 105° F. in water bath.

4. To one of each duplicate, add an additional 1 ppm (product) C.

5. Shake the bottles with a 3 inch stroke at 240 cps for 1 minute on amechanical shaker.

6. Place the bottles back into 105° F. bath.

7. Record degree to which an initial milky appearance forms.

8. Record the rate and degree the milky appearance disappears for 60minutes.

The results of this testing are presented in Table VIII.

                                      TABLE VIII                                  __________________________________________________________________________                Post Treatment Appearance Readings                                Treatment   5 Minutes   30 Minutes  60 Minutes                                Chemi-                                                                            ppm ppm     Bottom      Bottom      Bottom                                  cal orig add Top Oil Water I/F Top Oil Water I/F Top Oil Water I/F          __________________________________________________________________________    blank                                                                             0   0   trans-                                                                            clear,                                                                            very                                                                              trans-                                                                            clear,                                                                            much                                                                              trans-                                                                            clear                                                                             much                                   lucent, yellow much lucent, white soap parent, white soap                     brown  soap amber   amber                                                  A 6 0/0 trans- trans- much clear, clear, much clear, clear, little                                                          lucent, lucent, soap                                                      white white soap white white                                                  soap                                   brown amber                                                                A/C 6/0.3 0/0 trans- trans- much trans- clear, much trans- clear, much                                                      lucent, lucent, soap                                                      lucent, white soap parent,                                                    white soap                             brown brown  brown   amber                                                 A/C 6/0.6 0/0 trans- trans- much trans- clear, much trans- clear, much                                                      lucent, lucent, soap                                                      lucent, white soap lucent,                                                    white soap                             brown brown  brown   brown                                                 A/C 6/0.9 0/0 trans- trans- much trans- clear, much trans- clear, much                                                      lucent, lucent, soap                                                      lucent, white soap lucent,                                                    white soap                             brown brown  brown   brown                                                 H 4 0/0 trans- clear, little clear, clear, no clearer, clear, no                                                            parent, white soap white                                                  white soap white white soap                                                       yellow                          H/C 4/0.3 0/0 trans- clear, little clear, clear, no clearer, clear, no                                                      parent, white soap white                                                  white soap white white soap                                                       yellow                          H/C 4/0.6 0/0 trans- clear, little clear, clear, no clearer, clear, no                                                      parent, white soap white                                                  white soap white white soap                                                       yellow                          H/C 4/0.9 0/0 trans- clear, little clear, clear, no clearer, clear, no                                                      parent, white soap white                                                  white soap white white soap                                                       yellow                          B 4.6 0/0 trans- clear, no trans- clear, much clear, clear, little                                                          lucent, white soap                                                        parent, white soap yellow                                                     white soap                             brown   yellow                                                             B/C 4.6/0.3 0/0 trans- clear, no trans- clear, much trans- clear,                                                       little                                 lucent, white soap lucent, white soap lucent, white soap                      brown   brown   amber                                                      B/C 4.6/0.6 0/0 trans- clear, no trans- clear, much trans- clear, much                                                      lucent, white soap                                                        lucent, white soap lucent,                                                    white soap                             brown   brown   amber                                                      B/C 4.6/0.9 0/0 trans- clear, no trans- clear, much trans- clear, much                                                      lucent, white soap                                                        lucent, white soap lucent,                                                    white soap                             brown   brown   amber                                                      A/C 6/0 0/0.3 trans- trans- much trans- clear, much clear, clear, much                                                      lucent, lucent, soap                                                      lucent, white soap yellow                                                     white soap                             brown brown  brown                                                         A/C 6/0.3 0/0.3 trans- trans- much trans- clear, much trans- clear,                                                     much                                   lucent, lucent, soap lucent, white soap lucent, white soap                    brown brown  brown   amber                                                 A/C 6/0.6 0/0.3 trans- trans- much trans- clear, much trans- clear,                                                     much                                   lucent, lucent, soap lucent, white soap lucent, white soap                    brown brown  brown   amber                                                 A/C 6/0.9 0/0.3 trans- trans- much trans- clear, much trans- clear much          lucent, lucent, soap lucent, white soap lucent, white soap                    brown brown  brown   amber                                                 H/C 4/0 0/0.3 trans- clear, no clear, clear, no clearest clear, stays                                                       lucent, white soap white                                                  white soap white white clean                                                  on                                     amber        agit'n                                                        H/C 4/0.3 0/0.3 trans- clear, no clear, clear, no clearest clear, stays          lucent, white soap white white soap white white clean-                        amber        est on                                                                   agit'n*                                                            H/C 4/0.6 0/0.3 trans- clear, no clear, clear, no clearest clear, stays          lucent, white soap white white soap white white clean on                      amber        agit'n                                                        H/C 4/0.9 0/0.3 trans- clear, no clear, clear, no clearest clear, stays          lucent, white soap white white soap white white clean on                      amber        agit'n                                                        B/C 4.6/0 0/0.3 trans- trans- much trans- clear, much clear, clear,                                                     much                                   lucent, parent, soap lucent, white soap yellow white soap                     brown vesicles  brown                                                      B/C 4.6/0.3 0/0.3 trans- trans- much trans- clear, much trans- clear,                                                   much                                   lucent, parent, soap lucent, white soap parent, white soap*                   brown vesicles  brown   amber                                              B/C 4.6/0.6 0/0.3 trans- trans- much trans- clear, much trans- clear,                                                   much                                   lucent, parent, soap lucent, white soap parent, white soap                    brown vesicles  brown   amber                                              B/C 4.6/0.9 0/0.3 trans- trans- much trans- clear, much trans- clear,                                                   much                                   lucent, parent, soap lucent, white soap parent, white soap                    brown vesicles  brown   amber                                            __________________________________________________________________________     *Cleans up and doesn't redisperse after sitting overnight.               

These data demonstrate that treatment H at 4 ppm active or at 4 ppmactive combined in Stage 1 with Treatment C at 0.3 to 1.0 ppm activewould produce improved extraction (crystal clear top oil), less waste(crystal clear on bottom) and better process control and consistency(emulsion free interface in 30 minutes). The addition of an additional0.3 ppm active Treatment C in Stage 2 provides this all at an increasedthroughput capacity.

To find a more robust treatment capable of recovering from intermittentexcursions or cumulative retention of soap production and/orentrainment, such as the initial state to the system studied, arealistic amount of the accumulated emulsion withdrawn from theinterface of the 2nd stage, used in the initial testes (Table I and II),was added into each of the test bottles from the previous test andreshaken using the following procedure:

1. Add 2 mL 2nd stage interface emulsion to each bottle from previoustest

2. (Do not add more chemical treatment.)

3. Maintain at 105° F. in water bath.

4. Shake the bottles with a 3 inch stroke at 240 cps for 1 minute on amechanical shaker.

5. Place the bottles back into 105° F. bath.

6. Record degree to which an initial milky appearance forms.

7. Record the rate and degree the milky appearance disappears for 60minutes.

The results are shown in Table IX, where the treatment histories arethose of Table VIII.

                  TABLE IX                                                        ______________________________________                                               Post Treatment Appearance Readings                                     Treatment                                                                              30 Minutes      60 Minutes                                           Chemi-                                                                              ppm            Bottom            Bottom                                   cal total Top Oil Water I/F Top Oil Water I/F                               ______________________________________                                        blank 0      trans-  trans-                                                                              much  clear,                                                                              trans-                                                                              much                                 lucent, lucent, soap white lucent, soap                                       amber brown   brown                                                         A 6 trans- trans- much clear, trans- much                                       parent, lucent, soap white lucent, soap                                       yellow amber   brown                                                        A/C 6/ trans- trans- much clear, trans- much                                   0.3 parent, lucent, soap yellow lucent, soap                                   amber brown   brown                                                         A/C 6/ trans- trans- much trans- trans- much                                   0.6 lucent, lucent, soap parent, lucent, soap                                  amber brown  yellow brown                                                   A/C 6/ trans- trans- much trans- trans- much                                   0.9 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                    H 4 clear, trans- little clear, trans- little                                   yellow lucent, soap white lucent, soap                                         brown   amber                                                              H/C 4/ trans- trans- little clear, trans- little                               0.3 parent, lucent, soap white lucent, soap                                    yellow brown   amber                                                        H/C 4/ trans- trans- little clear, trans- little                               0.6 parent, lucent, soap white lucent, soap                                    yellow brown   amber                                                        H/C 4/ trans- trans- little clear, trans- little                               0.9 parent, lucent, soap white lucent, soap                                    amber brown   amber                                                         B 4.6 trans- trans- much clear, trans- much                                     parent, lucent, soap white lucent, soap                                       yellow brown   brown                                                        B/C 4.6/ trans- trans- much trans- trans- much                                 0.3 parent, lucent, soap parent, lucent, soap                                  amber brown  yeIIow brown                                                   B/C 4/6/ trans- trans- much trans- trans- much                                 0.6 parent, lucent, soap parent, lucent, soap                                  amber brown  yellow brown                                                   B/C 4.6/ trans- trans- much trans- trans- much                                 0.9 parent, lucent, soap parent, lucent, soap                                  amber brown  amber brown                                                    A/C 6/ trans- trans- much trans- trans- much                                   0.3 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                    A/C 6/ trans- trans- much trans- trans- much                                   0.6 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                    A/C 6/ trans- trans- much trans- trans- much                                   0.9 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                    A/C 6/ trans- trans- much trans- trans- much                                   1.2 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                    H/C 4/ trans- trans- little clear, trans- little                               0.3 parent, lucent, soap yellow parent, soap*                                  amber brown   amber                                                         H/C 4/ trans- trans- little trans- trans- little                               0.6 parent, lucent, soap parent, parent, soap                                  amber brown  yellow amber                                                   H/C 4/ trans- trans- little trans- trans- little                               0.9 parent, lucent, soap parent, parent, soap                                  amber brown  yellow amber                                                   H/C 4/ trans- trans- little trans- trans- little                               1.2 parent, lucent, soap parent, parent, soap                                  amber brown  yellow amber                                                   B/C 4.6/ trans- trans- much trans- trans- much                                 0.3 parent, lucent, soap parent, lucent, soap*                                 amber brown  yellow brown                                                   B/C 4.6/ trans- trans- much trans- trans- much                                 0.6 parent, lucent, soap parent, lucent, soap                                  amber brown  yellow brown                                                   B/C 4.6/ trans- trans- much trans- trans- much                                 0.9 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                    B/C 4.6/ trans- trans- much trans- trans- much                                 1.2 lucent, lucent, soap lucent, lucent, soap                                  brown brown  amber brown                                                  ______________________________________                                         *no soap on reshaking after sitting overnight.                           

These data demonstrate the Treatment H by itself at 4 ppm activeclarified the oil the fastest. This treatment combined with treatment Cat 0.3 ppm active in Stage 2 was almost as fast, produced the cleanestwater and was the best treatment on reshaking after sitting overnight (ameasure of complete interfacial emulsion resolution/emulsifier removalwhen detained at the interface of the process vessels).

To measure the effects of these extraction aids on an actual POSM washunit, a 30 day trial was conducted. The throughput of crude styrene wasvaried to optimize the treatment under various conditions. The build upof soapy emulsion was monitored in both stages by examining samplestaken from the mid vessel trilines. Extraction performance was measuredby analyzing the second stage effluent oil for free phenol, by GC, andsodium, by AA, and by measuring the water removed from the overheadaccumulator in the downstream styrene distillation unit.

Treatment H was fed at 2 to 6 ppm active to the first stage influentstyrene. Treatment C was fed at 0.3 to 0.5 ppm active to either thesecond stage influent water or the aqueous influents to both stages.

These results are reported in Table X.

                                      TABLE X                                     __________________________________________________________________________    Styrene Rate                                                                             Baseline  Low Rate Test  High Rate Test                            (MPPH)     208  180  167 167 167                                                                              167 214 214 214                               __________________________________________________________________________    H to Stage 1 (ppm Act)                                                                   0    0    4   4   6  2   2   4   6                                   C to Stage 1 (ppm Act) 0 0 0 0.3 .03 0.3 0.3 0.4 0.5                          C to Stage 2 (ppm Act) 0 0 0.3 0.3 0.3 0.3 0.3 0.4 0.5                        Trilines of Stable 3-4 2-4 2.0 0.5 1.0 0.5 1.0 0.5 0.5                        Emulsion St. 1 (#) avg. 3.5 avg. 3.0                                          Trilines of Stable 3-4 2-4 0.5 0.5 .05 0.5 1.0 0.5 0.5                        Emulsion St. 2 (#) avg. 3.5 avg. 3.0                                          Frequency of I/F 4 1 0 0 0 0 0 0 0                                            Dumpings (#/mo.)                                                            Water Distilled                                                                          600-2400                                                                           200-2000                                                                           150-550, avg. 350                                                                            500-900, avg. 700                           Overhead (PPH) avg 1300 avg. 900                                              Na in Washed 2-55 5-9 2-8, avg. 5 2-6, avg. 4                                 Styrene (ppm) avg. 10 avg. 7                                                Phenol in Washed                                                                         6-12 2-6  2-4 2-3 2  2-3 3-5 5-7 5                                   Styrene (ppm) avg. 9 avg. 4 avg. 3 avg. 2.5  avg. 2.5 avg. 4 avg.           __________________________________________________________________________                                                6                             

These data demonstrate that the co-addition of these two extraction aidsimproved the conversion of phenol to Na phenate while also improving theremoval of phenates to the water or interface, and the dissolution ofthe phenate soaps into the water. This improved the quality of thefinished styrene monomer and eliminated the withdrawal and disposal ofstable emulsion.

While this invention has been described with respect to particularembodiments thereof, it is apparent that numerous other forms andmodifications of this invention will be obvious to those skilled in theart. The appended claims and this invention generally should beconstrued to cover all such obvious forms and modifications which arewithin the true spirit and scope of the present invention.

Having thus described the invention, what I claim is:
 1. An improvedmethod for extracting phenols from crude styrene with an aqueous causticsolution, the improvement comprising adding an effective amount ofaromatic ammonium tailed multi-polyether headed surfactant oralkylammonium tailed multi-polyether headed surfactant or quaternarypolyamine to extract phenols from said crude styrene.
 2. The method asclaimed in claim 1 wherein said aromatic or alkylammonium tailedmulti-polyether headed surfactants are selected from the groupconsisting of those surfactants having hydrophobic "tails" of C₃ to C₁₈alkylaryl diols to polyols and C₃ to C₂₂ alkyl or alkylaryl 1° or 2°amines adducted with C₂ to C₃ alkylene oxides to form two or morehydrophilic "heads" per hydrophobe having separate polyether chains ofdegree of polymerization 3 to 30 and the backbone and branches of thepolymer contain only either or amine linkages.
 3. The method as claimedin claim 2 wherein said aromatic tailed multi-polyether headedsurfactants are selected from the group consisting of C₄ to C₉alkylphenol-formaldehyde condensates of degree of polymerization 4 to 8adducted with ethylene oxide to form 4 to 8 polyether chains of degreeof polymerization 4 to 7 blended with alkylammonium tailedmulti-polyether headed surfactants selected from the group consisting ofthe halide salts of linear C₁₂ to C₂₂ alkyl 2° amines adducted withethylene oxide to form 2 polyether chains of degree of polymerization 5to
 10. 4. The method as claimed in claim 1 wherein said quaternarypolyamine has a backbone and branches containing only ether or aminelinkages.
 5. The method as claimed in claim 4 wherein said quaternarypolyamine has a degree of polymerization of about 60 to 60,000 monomerunits.
 6. The method as claimed in claim 1 wherein said quaternarypolyamine has an overall carbon to nitrogen or oxygen ratio of less than10.
 7. The method as claimed in claim 1 wherein said quaternarypolyamine is selected from the group consisting of halides, sulfates,nitrates, phosphates, carboxylates, phenates, silicates, carbonates orhydroxides of alkyl or alkylaryl quaternary amines.
 8. The method asclaimed in claim 7 wherein said quaternary polyamine is selected fromthe group consisting of poly(diallydimethylammonium chloride),poly(N,N-dimethyl, 2-hydroxypropyleneammonium chloride), andpoly(N,N-dimethyl, 3-(2-hydroxypropyleneamine) propylammonium chloride).9. The method as claimed in claim 1 wherein said multi-polyether headedsurfactant is fed to said styrene in a solvent selected from the groupconsisting of high boiling aromatic hydrocarbons, glycol ethers andaromatic alcohols.
 10. The method as claimed in claim 1 wherein saidmulti-polyether headed surfactant is added to influent unwashed styrene.11. The method as claimed in claim 1 wherein said multi-polyether headedsurfactant is added to styrene that is washed but not rinsed.
 12. Themethod as claimed in claim 1 wherein said multi-polyether headedsurfactant is added in an amount ranging from 3 parts to about 30 partsper million parts of styrene.
 13. The method as claimed in claim 1wherein said quaternary polyamine is added as an aqueous solution toinfluent caustic wash water or both fresh rinse water and influentcaustic wash water.
 14. The method as claimed in claim 1 wherein saidquaternary polyamine is added to water in an amount ranging from about 1to about 100 parts of polyamine per million parts of water.
 15. Themethod as claimed in claim 1 wherein said styrene is present in apropylene oxide styrene monomer process.